2-[4-(Methyl­sulfon­yl)phen­yl]acetonitrile

Fun, H.-K.; Quah, C.K.; Sumangala, V.; Prasad, D.J.; Poojary, B.

doi:10.1107/S1600536811003837

organic compounds

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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o574

doi:10.1107/S1600536811003837

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2-[4-(Methylsulfonyl)phenyl]acetonitrile

Hoong-Kun Fun,^a ^*‡ Ching Kheng Quah,^a § V. Sumangala,^b D. Jagadeesh Prasad ^b and Boja Poojary ^b

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bDepartment of Chemistry, Mangalore University, Mangalagangotri, Karnataka State 574 199, India
^*Correspondence e-mail: hkfun@usm.my

(Received 26 January 2011; accepted 30 January 2011; online 5 February 2011)

In the title compound, C₉H₉NO₂S, the benzene ring and the acetonitrile group are approximately coplanar, with a C—C—C—C torsion angle of 1.1 (3)° between them. In the crystal, molecules are linked via intermolecular C—H⋯O hydrogen bonds into layers parallel to (001).

Related literature

For general background to and the biological activity of COX-2 inhibitors, see: Orjales et al. (2008 ); Zarghi et al. (2008 ); Shah et al. (2010 ); Arico et al. (2002 ); Davies et al. (2002 ); Sawaoka et al. (1998 ); Liu et al. (2000 ); Pasinetti (2001 ); Norman et al. (1995 ). For a related structure, see: Charlier et al. (2004 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₉H₉NO₂S
M_r = 195.23
Triclinic, $[P \overline 1]$
a = 5.5599 (2) Å
b = 8.0942 (3) Å
c = 10.9006 (4) Å
α = 81.162 (2)°
β = 85.347 (2)°
γ = 74.458 (2)°
V = 466.60 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 296 K
0.51 × 0.28 × 0.14 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.810, T_max = 0.957
5970 measured reflections
1826 independent reflections
1673 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.110
S = 1.09
1826 reflections
119 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5A⋯O1ⁱ	0.93	2.47	3.384 (2)	169
C9—H9B⋯O2ⁱⁱ	0.96	2.39	3.343 (3)	175
Symmetry codes: (i) x, y-1, z; (ii) x+1, y, z.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811003837/is2671sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811003837/is2671Isup2.hkl

checkCIF report

Comment top

Compounds bearing the 4-methylsulfonylphenyl moiety are found to possess diverse biological properties. They are found to be highly potent and specific COX-2 inhibitors (Orjales et al., 2008; Zarghi et al., 2008; Shah et al., 2010). Recent studies have shown that selective COX-2 inhibitors can induce apoptosis in colon, stomach, prostate, and breast cancer cell lines (Arico et al., 2002; Davies et al., 2002; Sawaoka et al., 1998; Liu et al., 2000). Selective COX-2 inhibitors offer potential treatment for the prophylactic prevention of inflammatory neurodegerative disorders such as Alzheimer's disease (Pasinetti, 2001). They are also found to be anti-inflammatory agents (Norman et al., 1995). The crystal structure of a methylsulfonylphenyl derivative has been reported (Charlier et al., 2004).

The molecular structure is shown in Fig. 1. Bond lengths (Allen et al., 1987) and angles are within normal ranges. The benzene ring (C1–C6) and the acetonitrile group (C7/C8/N1) are approximately coplanar [torsion angles C1—C6—C7—C8 = 1.1 (3) and C5—C6—C7—C8 = -178.67 (16) °]. In the crystal packing (Fig. 2), the molecules are linked via intermolecular C5–H5A···O1 and C9–H9B···O2 (Table 1) hydrogen bonds into infinite two-dimensional planes parallel to (001).

Related literature top

For general background to and the biological activity of COX-2 inhibitors, see: Orjales et al. (2008); Zarghi et al. (2008); Shah et al. (2010); Arico et al. (2002); Davies et al. (2002); Sawaoka et al. (1998); Liu et al. (2000); Pasinetti (2001); Norman et al. (1995). For a related structure, see: Charlier et al. (2004). For bond-length data, see: Allen et al. (1987).

Experimental top

4-Methylthiophenylacetonitrile (0.1 mol) was taken in 3 mL of acetic anhydride and cooled to 5°C. To the reaction mixture sodium tungstate (0.02 mol) was added followed by 30% hydrogen peroxide (0.2 mol) in 1.2 mL of acetic acid and water mixture (in 2:1 ratio). The temperature of the reaction mixture was slowly brought to room temperature. The completion of reaction was monitored by TLC. The solid precipitate was filtered and washed with water until the pH became neutral. The product was dried at 65 °C for 10-12 h. The product was then recrystallized in methanol (m. p.: 120–124 °C).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008; molecular graphics: SHELXTL (Sheldrick, 2008; software used to prepare material for publication: SHELXTL (Sheldrick, 2008 and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound showing 30% probability displacement ellipsoids for non-H atoms and the atom-numbering scheme.
	Fig. 2. The crystal structure of the title compound, viewed along the c axis. H atoms not involved in hydrogen bonds (dashed lines) have been omitted for clarity.

2-[4-(Methylsulfonyl)phenyl]acetonitrile top

Crystal data top

C₉H₉NO₂S	Z = 2
M_r = 195.23	F(000) = 204
Triclinic, P1	D_x = 1.390 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.5599 (2) Å	Cell parameters from 4240 reflections
b = 8.0942 (3) Å	θ = 2.6–33.0°
c = 10.9006 (4) Å	µ = 0.31 mm⁻¹
α = 81.162 (2)°	T = 296 K
β = 85.347 (2)°	Block, colourless
γ = 74.458 (2)°	0.51 × 0.28 × 0.14 mm
V = 466.60 (3) Å³

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1826 independent reflections
Radiation source: fine-focus sealed tube	1673 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −6→6
T_min = 0.810, T_max = 0.957	k = −9→9
5970 measured reflections	l = −13→13

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.054P)² + 0.1771P] where P = (F_o² + 2F_c²)/3
1826 reflections	(Δ/σ)_max = 0.001
119 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

C₉H₉NO₂S	γ = 74.458 (2)°
M_r = 195.23	V = 466.60 (3) Å³
Triclinic, P1	Z = 2
a = 5.5599 (2) Å	Mo Kα radiation
b = 8.0942 (3) Å	µ = 0.31 mm⁻¹
c = 10.9006 (4) Å	T = 296 K
α = 81.162 (2)°	0.51 × 0.28 × 0.14 mm
β = 85.347 (2)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1826 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1673 reflections with I > 2σ(I)
T_min = 0.810, T_max = 0.957	R_int = 0.023
5970 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 1.09	Δρ_max = 0.29 e Å⁻³
1826 reflections	Δρ_min = −0.42 e Å⁻³
119 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.64766 (8)	0.30347 (6)	0.36428 (4)	0.04502 (19)
O1	0.6714 (4)	0.45775 (18)	0.28743 (16)	0.0728 (5)
O2	0.4011 (3)	0.2889 (2)	0.40261 (19)	0.0773 (5)
N1	1.5750 (4)	−0.2897 (2)	−0.02043 (19)	0.0638 (5)
C1	1.1353 (3)	−0.0135 (2)	0.15700 (17)	0.0427 (4)
H1A	1.2799	−0.0114	0.1081	0.051*
C2	1.0162 (3)	0.1282 (2)	0.21644 (17)	0.0429 (4)
H2A	1.0801	0.2246	0.2080	0.051*
C3	0.8008 (3)	0.1237 (2)	0.28841 (15)	0.0365 (4)
C4	0.7055 (3)	−0.0194 (2)	0.30170 (17)	0.0439 (4)
H4A	0.5607	−0.0212	0.3505	0.053*
C5	0.8260 (3)	−0.1598 (2)	0.24231 (18)	0.0445 (4)
H5A	0.7620	−0.2561	0.2512	0.053*
C6	1.0422 (3)	−0.1580 (2)	0.16938 (15)	0.0370 (4)
C7	1.1679 (4)	−0.3160 (2)	0.10645 (18)	0.0464 (4)
H7A	1.2073	−0.4167	0.1694	0.056*
H7B	1.0511	−0.3343	0.0517	0.056*
C8	1.3966 (4)	−0.3021 (2)	0.03441 (18)	0.0468 (4)
C9	0.8180 (4)	0.2777 (3)	0.4977 (2)	0.0586 (5)
H9A	0.7482	0.3732	0.5433	0.088*
H9B	0.9891	0.2744	0.4738	0.088*
H9C	0.8100	0.1716	0.5490	0.088*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0405 (3)	0.0414 (3)	0.0506 (3)	−0.00199 (19)	−0.00442 (19)	−0.0129 (2)
O1	0.1054 (14)	0.0367 (8)	0.0691 (10)	−0.0059 (8)	−0.0101 (9)	−0.0042 (7)
O2	0.0381 (8)	0.0876 (12)	0.1116 (14)	−0.0088 (7)	0.0091 (8)	−0.0496 (11)
N1	0.0653 (12)	0.0591 (11)	0.0703 (12)	−0.0208 (9)	0.0182 (10)	−0.0217 (9)
C1	0.0428 (9)	0.0427 (10)	0.0458 (10)	−0.0169 (7)	0.0069 (7)	−0.0099 (7)
C2	0.0466 (10)	0.0382 (9)	0.0479 (10)	−0.0185 (7)	0.0028 (8)	−0.0079 (7)
C3	0.0367 (8)	0.0361 (8)	0.0354 (8)	−0.0072 (7)	−0.0024 (6)	−0.0042 (6)
C4	0.0390 (9)	0.0468 (10)	0.0474 (10)	−0.0153 (8)	0.0042 (7)	−0.0070 (8)
C5	0.0471 (10)	0.0393 (9)	0.0519 (10)	−0.0200 (8)	−0.0002 (8)	−0.0062 (8)
C6	0.0395 (9)	0.0366 (8)	0.0351 (8)	−0.0094 (7)	−0.0051 (7)	−0.0050 (7)
C7	0.0500 (10)	0.0394 (9)	0.0516 (11)	−0.0119 (8)	−0.0004 (8)	−0.0123 (8)
C8	0.0567 (12)	0.0381 (9)	0.0463 (10)	−0.0094 (8)	−0.0016 (9)	−0.0138 (8)
C9	0.0550 (12)	0.0689 (14)	0.0505 (11)	−0.0037 (10)	−0.0073 (9)	−0.0231 (10)

Geometric parameters (Å, º) top

S1—O1	1.4239 (16)	C4—C5	1.381 (3)
S1—O2	1.4306 (16)	C4—H4A	0.9300
S1—C9	1.755 (2)	C5—C6	1.388 (2)
S1—C3	1.7657 (17)	C5—H5A	0.9300
N1—C8	1.136 (3)	C6—C7	1.519 (2)
C1—C6	1.385 (2)	C7—C8	1.461 (3)
C1—C2	1.387 (2)	C7—H7A	0.9700
C1—H1A	0.9300	C7—H7B	0.9700
C2—C3	1.383 (2)	C9—H9A	0.9600
C2—H2A	0.9300	C9—H9B	0.9600
C3—C4	1.382 (3)	C9—H9C	0.9600

O1—S1—O2	117.73 (12)	C4—C5—H5A	119.8
O1—S1—C9	108.35 (11)	C6—C5—H5A	119.8
O2—S1—C9	108.32 (12)	C1—C6—C5	119.12 (16)
O1—S1—C3	108.95 (9)	C1—C6—C7	122.56 (16)
O2—S1—C3	108.26 (9)	C5—C6—C7	118.32 (15)
C9—S1—C3	104.42 (9)	C8—C7—C6	113.81 (15)
C6—C1—C2	120.95 (16)	C8—C7—H7A	108.8
C6—C1—H1A	119.5	C6—C7—H7A	108.8
C2—C1—H1A	119.5	C8—C7—H7B	108.8
C3—C2—C1	118.95 (16)	C6—C7—H7B	108.8
C3—C2—H2A	120.5	H7A—C7—H7B	107.7
C1—C2—H2A	120.5	N1—C8—C7	179.0 (2)
C4—C3—C2	120.80 (16)	S1—C9—H9A	109.5
C4—C3—S1	119.91 (13)	S1—C9—H9B	109.5
C2—C3—S1	119.28 (13)	H9A—C9—H9B	109.5
C5—C4—C3	119.72 (16)	S1—C9—H9C	109.5
C5—C4—H4A	120.1	H9A—C9—H9C	109.5
C3—C4—H4A	120.1	H9B—C9—H9C	109.5
C4—C5—C6	120.45 (16)

C6—C1—C2—C3	−0.3 (3)	C2—C3—C4—C5	−0.1 (3)
C1—C2—C3—C4	0.3 (3)	S1—C3—C4—C5	−179.93 (13)
C1—C2—C3—S1	−179.94 (13)	C3—C4—C5—C6	0.0 (3)
O1—S1—C3—C4	−145.12 (16)	C2—C1—C6—C5	0.1 (3)
O2—S1—C3—C4	−15.97 (18)	C2—C1—C6—C7	−179.65 (16)
C9—S1—C3—C4	99.29 (17)	C4—C5—C6—C1	0.0 (3)
O1—S1—C3—C2	35.06 (17)	C4—C5—C6—C7	179.80 (16)
O2—S1—C3—C2	164.22 (15)	C1—C6—C7—C8	1.1 (3)
C9—S1—C3—C2	−80.53 (17)	C5—C6—C7—C8	−178.67 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···O1ⁱ	0.93	2.47	3.384 (2)	169
C9—H9B···O2ⁱⁱ	0.96	2.39	3.343 (3)	175

Symmetry codes: (i) x, y−1, z; (ii) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₉H₉NO₂S
M_r	195.23
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	5.5599 (2), 8.0942 (3), 10.9006 (4)
α, β, γ (°)	81.162 (2), 85.347 (2), 74.458 (2)
V (Å³)	466.60 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.51 × 0.28 × 0.14

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.810, 0.957
No. of measured, independent and observed [I > 2σ(I)] reflections	5970, 1826, 1673
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.110, 1.09
No. of reflections	1826
No. of parameters	119
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.42

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008 and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···O1ⁱ	0.93	2.47	3.384 (2)	169
C9—H9B···O2ⁱⁱ	0.96	2.39	3.343 (3)	175

Symmetry codes: (i) x, y−1, z; (ii) x+1, y, z.

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Thomson Reuters ResearcherID: A-5525-2009.

Acknowledgements

HKF and CKQ thank Universiti Sains Malaysia for the Research University Grant (No. 1001/PFIZIK/811160).

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